## PS3-

 S3 \\ P1 = S2 // S4
The ion charge is -1.

## Atomic Charges and Dipole Moment

P1 charge= 0.339
S2 charge=-0.446
S3 charge=-0.446
S4 charge=-0.446
with a dipole moment of 0.00619 Debye

## Bond Lengths:

between P1 and S2: distance=1.999 ang___ between P1 and S3: distance=1.999 ang___
between P1 and S4: distance=1.999 ang___

## Bond Angles:

for S3-P1-S2: angle=120.0 deg___ for S4-P1-S2: angle=120.1 deg___

## Bond Orders (Mulliken):

between P1 and S2: order=1.364___ between P1 and S3: order=1.366___
between P1 and S4: order=1.365___

## Best Lewis Structure

The Lewis structure that is closest to your structure is determined. The hybridization of the atoms in this idealized Lewis structure is given in the table below. Please note that your structure can't be well described by a single Lewis structure, because of extensive delocalization.

### Hybridization in the Best Lewis Structure

1. A bonding orbital for P1-S2 with 1.9823 electrons
__has 50.09% P 1 character in a sp1.96 hybrid
__has 49.91% S 2 character in a s0.54 p3 hybrid

2. A bonding orbital for P1-S3 with 1.9823 electrons
__has 50.08% P 1 character in a sp1.97 hybrid
__has 49.92% S 3 character in a s0.54 p3 hybrid

3. A bonding orbital for P1-S4 with 1.9980 electrons
__has 20.72% P 1 character in a p-pi orbital ( 97.80% p 2.20% d)
__has 79.28% S 4 character in a p-pi orbital ( 99.71% p 0.29% d)

4. A bonding orbital for P1-S4 with 1.9823 electrons
__has 50.09% P 1 character in a sp1.96 hybrid
__has 49.91% S 4 character in a s0.54 p3 hybrid

5. A antibonding orbital for S2-S3 with 1.9829 electrons
__has 50.01% S 2 character in a p-pi orbital ( 99.80% p 0.20% d)
__has 49.99% S 3 character in a p-pi orbital ( 99.80% p 0.20% d)

6. A bonding orbital for S2-S3 with 1.4117 electrons
__has 49.99% S 2 character in a p-pi orbital ( 99.80% p 0.20% d)
__has 50.01% S 3 character in a p-pi orbital ( 99.80% p 0.20% d)

27. A lone pair orbital for S2 with 1.9784 electrons

28. A lone pair orbital for S2 with 1.9090 electrons
__made from a p-pi orbital ( 99.88% p 0.12% d)

29. A lone pair orbital for S3 with 1.9785 electrons

30. A lone pair orbital for S3 with 1.9093 electrons
__made from a p-pi orbital ( 99.88% p 0.12% d)

31. A lone pair orbital for S4 with 1.9784 electrons

32. A lone pair orbital for S4 with 1.9092 electrons
__made from a p-pi orbital ( 99.88% p 0.12% d)

123. A antibonding orbital for P1-S4 with 0.5488 electrons
__has 79.28% P 1 character in a p-pi orbital ( 97.80% p 2.20% d)
__has 20.72% S 4 character in a p-pi orbital ( 99.71% p 0.29% d)

-With core pairs on: P 1 P 1 P 1 P 1 P 1 S 2 S 2 S 2 S 2 S 2 S 3 S 3 S 3 S 3 S 3 S 4 S 4 S 4 S 4 S 4 -

#### Donor Acceptor Interactions in the Best Lewis Structure

The localized orbitals in your best Lewis structure can interact strongly. A filled bonding or lone pair orbital can act as a donor and an empty or filled bonding, antibonding, or lone pair orbital can act as an acceptor. These interactions can strengthen and weaken bonds. For example, a lone pair donor->antibonding acceptor orbital interaction will weaken the bond associated with the antibonding orbital. Conversly, an interaction with a bonding pair as the acceptor will strengthen the bond. Strong electron delocalization in your best Lewis structure will also show up as donor-acceptor interactions.
Interactions greater than 20 kJ/mol for bonding and lone pair orbitals are listed below.

The interaction of bonding donor orbital, 3, for P1-S4 with the bonding acceptor orbital, 6, for S2-S3 is 32.3 kJ/mol.

The interaction of bonding donor orbital, 6, for S2-S3 with the antibonding acceptor orbital, 123, for P1-S4 is 860. kJ/mol.

The interaction of the second lone pair donor orbital, 28, for S2 with the antibonding acceptor orbital, 122, for P1-S3 is 53.2 kJ/mol.

The interaction of the second lone pair donor orbital, 28, for S2 with the second antibonding acceptor orbital, 124, for P1-S4 is 53.3 kJ/mol.

The interaction of the second lone pair donor orbital, 30, for S3 with the antibonding acceptor orbital, 121, for P1-S2 is 53.1 kJ/mol.

The interaction of the second lone pair donor orbital, 30, for S3 with the second antibonding acceptor orbital, 124, for P1-S4 is 53.0 kJ/mol.

The interaction of the second lone pair donor orbital, 32, for S4 with the antibonding acceptor orbital, 121, for P1-S2 is 53.3 kJ/mol.

The interaction of the second lone pair donor orbital, 32, for S4 with the antibonding acceptor orbital, 122, for P1-S3 is 53.0 kJ/mol.

## Molecular Orbital Energies

The orbital energies are given in eV, where 1 eV=96.49 kJ/mol. Orbitals with very low energy are core 1s orbitals. More antibonding orbitals than you might expect are sometimes listed, because d orbitals are always included for heavy atoms and p orbitals are included for H atoms. Up spins are shown with a ^ and down spins are shown as v.

36 ----- 4.916 35 ----- 4.905

34 ----- 2.084

33 ----- 1.136

32 -^-v- -0.929

31 -^-v- -1.840 30 -^-v- -1.843

29 -^-v- -2.057 28 -^-v- -2.058

27 -^-v- -4.363

26 -^-v- -5.071 25 -^-v- -5.074

24 -^-v- -7.995

23 -^-v- -12.74 22 -^-v- -12.75

21 -^-v- -15.40

20 -^-v- -120.9 19 -^-v- -120.9

18 -^-v- -121.1

17 -^-v- -149.8 16 -^-v- -149.8 15 -^-v- -149.8

14 -^-v- -150.0 13 -^-v- -150.0 12 -^-v- -150.0

11 -^-v- -150.2 10 -^-v- -150.2 9 -^-v- -150.2

8 -^-v- -168.5

7 -^-v- -202.9 6 -^-v- -202.9 5 -^-v- -202.9

4 -^-v- -2066.

3 -^-v- -2382. 2 -^-v- -2382. 1 -^-v- -2382.

## Total Electronic Energy

The total electronic energy is a very large number, so by convention the units are given in atomic units, that is Hartrees (H). One Hartree is 2625.5 kJ/mol. The energy reference is for totally dissociated atoms. In other words, the reference state is a gas consisting of nuclei and electrons all at infinite distance from each other. The electronic energy includes all electric interactions and the kinetic energy of the electrons. This energy does not include translation, rotation, or vibration of the the molecule.

Total electronic energy = -1536.2421097176 Hartrees